Photographic product for forming a transfer image



y 19, 1953 E. H. LAND 2,639,233

PHOTOGRAPHIC PRODUCT FOR FORMING A TRANSFER IMAGE Original Filed June 9, 1944 2 sneaks-sheet 1 Porous Layer Trqnspureni Bose Image Receiving Layer Phoiosensflive Layer Li quid Coniuining qnd Dishibufing Means 38 42 4O 44 Frungible Liquid-Rewinding Wall Wqier-Vupor lmpervious Coqfing EXPOSE AND RELEASE LIQUID Liquid Coniaining Layer Posiiive Image Transfer Prini OBTAIN TRANS INV TOR May 19, 1953 E. H. LAND 2, 3

PHOTOGRAPHIC PRODUCT FOR FORMING A TRANSFER IMAGE Original Filed June 9, 1944 2 Sheets-Sheet 2 Phoiosensifive Layer Base Member Base Permeable AnH-Halcfion Coafing posmve lmoge Receiving Layer FIG. 3

L196 :R\ I){\ 98 96 94 G 4 96 94 INVEN R fw M BY m Patented May 19, 1953 UNITED STATES" PATENT OFFICE PHOTOGRAPHIC PRODUCT FOR FORMING A TRANSFER, IMAGE Edwin H. Land, Cambridge, Mass, assignor to Polaroid Corporation, Cambridge, Mass., a corporation of Delaware I Original application June 9, 1944, Serial No.

-- 539,550. Divided'and this application February 1, 1949, Serial N0. 73,961

I 19 Claims. (01. 95--8) This invention relates to photography and more particularly to photographic products whereina liquid is contained for processing a photographic hotosensitive material.

.This invention is a division of-my copending application Serial No. 539,550, filed June 9, 1944,

for Photographic Product (now abandoned).

One object of the present invention is to provide a novel photographic product in the form of a rupturable disposable container releasably carryingea photographic processing liquid and so constructed as to be able, upon application of a suitablestress thereto,-to release its liquid content for substantially uniform distribution over a predetermined area of a photosensitive material to process the same. 1

Anotherobject of the present invention is to provide a product of the foregoing character which isfsheetlike in'shape and which comprises a liquid-containing stratum or'layer and a rupturable liquid-retaining member superposed thereon. c r

Still another object is the-provision of a photographic product which contains all of the liquid and all of the reagents required to develop a. Y developable, photosensitive element.

Other objects of the invention will in part be obvious and will in part appear hereinafter.

The invention accordingly comprises the product possessing the features, properties and the v,relation of components which are exemplified in the following detailed disclosure, and the scope of the application of which will be indicated in theclaims.

v For a fuller understanding of the nature and objects of the invention, reference should be had to the following detailed. description taken in connection with the accompanying drawings wherein:

7 Figure 1 consists of four enlarged, diagrammatic, fragmentary sectional views of four stages in the formation of a print bythe use of one form of the liquid-containing product of the present invention;

Fig. 2 is an enlarged diagrammatic, fragmen-, tary sectional view of a modification of the novel liquid-containing means shown in the first stage of Fig; 1; 1

Fig. 3 is a view, .similarto Fig. 2, of another composite film embodying, as an element thereof,-

the novel'liquid-containing means of the invention;

- Fig. use. -.view similar to Fig.2bfstil1 another embodiment 'Iof the liquid-containing meansof ...thelatterfigur q Fig. 5 is adiagrammatic view, partly in section and partly in elevation, with parts broken away, of apparatus for filling the cells of the fluidcontaining member of Fig. 4.

Referring to Fig. 1 there is illustrated diagrammatically a photographic film which embodies as an element thereof the containing means of the present invention, said film as shown comprising a suitable base 32 formed of a transparent material, preferably a plastic, such as a cellulosic ester,

or a synthetic superpolymer of the nylon type, a layer 34 of clear gelatin, polyvinyl alcohol or other transparent material wherein a positive image may be'formed, and a layer 36 of photosensitive material such as a silver halide gelatin emulsion, said layers being superimposed upon the base in the order named.

- membrane 42 formed, brittle plastic such as .layer 36, and a ethylene, is coated on the other Film 44 forms apartof a casing which completely The film-is provided with novel liquid-containing means 38 which, as illustrated, comprise a.

. sheet of porous material such as blotter paper,

containing within its pores a predetermined quantity of at least the solvent, e. g., water, for the liquid reagent. I To retain the liquid within said sheet a frangible liquid-retaining wall or for example, of a relatively polystyrene, is laminated to one face of said sheet between the latter and thin film 44 of water vaporimpervious material, such as parafiin or polyside of said sheet.

encloses sheet 4|] and prevents loss by vaporization of the liquid content of said sheet. As

shown, a layer of the vapor-impervious material forms anouter coating 46 for base 32, but it is equally possible to employ a vapor-impervious plastic, such as polyethylene, as the base 32 and to connect said base with layer 44 by an edge seal to provide the vapor-impervious casing.

To release the liquid from sheet i0, membrane 422 is fractured as by being stretched beyond its yield point. In order to provide a deformable base against which said membrane may be fractured, and to insure a uniform permeation of photosensitive layer 36 by the reagent when the latter is released, a porous layer 48, for example,

of the same material as sheet 40, is located between membrane 42 and said photosensitive layer.

It is to be understood that layer 48 may contain in solid form one or more of the compounds for 'the liquid reagent, which compounds are dissolved in the liquid as it passes through said layer.

All'of'the above described layers are laminated together in any suitable manner to form the film .1555. and layer 36 .is secured to layer 34 so that separation of the two film portions on opposite sides of the interface of said layers may be readily effected. It is to be expressly understood that the drawings are diagrammatic and that the layer thicknesses are not drawn to scale. The overall thickness of the film may vary from a thickness somewhat greater than, to a thickness several times that of, ordinary photographic One method of forming a fixed image in accordance with the present invention is to provide within means 38 a liquid reagent and to provide in said reagent a developer, e. g., hydro'quinone, and a compound, e. g., sodium thiosulfate, which forms soluble complex ions with silver halide at a less rapid rate than the developer will develop exposed silver halide. To carry out the method, a frame of the film is differentially exposed to actinic light, as for example in a camera, so that a, latent image is formed in layer 36. After exposure, membrane 42 is fractured to cause the -liquid reagent'to permeate layer 36 (Fig.1). At-exposed areas 50 of said layer, development takes place and the silver halide is reduced to silver, remaining in layer 35, Whereas at unexpcsedareas 5?. the silver halide forms a soluble complex and is transported at least in part by the reagent to adjacent positive print layer 34 where reduction of the complex silver ions in solution is effected by the developer to form areas 54 of silver, the latter areas corresponding to the unexposed areas 52 of layer 36. An

image is thus produced which is the positive of the latent image formed in photosensitive layer 35, and in order to provide a White opaque background for such image'the surface layer of base 32 adjoining layer 34 has dispersed thereon or therein a colorless compound which reacts with a compound contained in the liquid reagent to form a layer 56 of the white precipitate '(Fig. 1). It is to be'understood that the colorless compound may also be contained in asuitablc permeable, transparent layer, for example of gelatin, disposed between base 32 and layer 34.

If a positive transparency is desired instead of a print with an opaque background, one or both of the above compounds for producing layer 56 may be eliminated from the film.

The positive print (last stage of Fig. 1) comprising a silver image on a white or transparent background, as desired, is obtained by stripping base 32 together with layer 34 from the remaintier of the film, as shown in the third stage of Fig. 1.

It will be noted that the print thus obtained is corrected for geometric reversal.

Inthe above described embodiment, the developer and the other reactive ingredients of the reagent may be contained either in layer 48 or in the liquid in layer 40. It is also possible tc-provide one or more of these materials in solid form in photosensitive layer 36, but this procedure is not preferred because it will tend to desensitize said layer.

An example of a liquid reagent suitable for permeating the photosensitive layer in order to carry out the above method is one consisting of:

Water to make 170 cc.

, A modification so or the liquid-containing 4 means 38 of Fig. 1 is shown in Fig. 2 and comprises a plurality of cells or chambers 62 formed by a plurality of grooves 64 in a base member 66, such as a sheet of cellulose acetate or cellulose nitrate; said grooves bein'g prei'erably filled with the liquid and sealed by a frangible membrane or wall 68 formed, for example, of polystyrene and corresponding in function and structure to membrane 42 of the film of Fig. 1. Liquid-con taming means Ell may be substituted for means as and if desired a porous layer, corresponding to layer 48 of the film of Fig. 1, may be provided between membrane 68 and layer 36 when means 60 is so substituted.

It is to be understood that cells 62 of developerretaining means 60 may be of various shapes, as

7 for example rectangular or substantially circutranslated to a positive print layer from a photolar in cross-section. It is preferable too that grooves 64 do not extend continuously across the film, so that in each transverse row of said grooves there is provided a plurality of cells. Moreover, the cells of successivezrows are staggered so that the film can be cut longitudinally into strips afterthe cells are filled, for example during the manufacture of the film, without appreciable loss of liquid, and without rendering the strips thus obtained inoperative.

Referring to Fig. 3, there is illustrated another modification of the novel film means of the present invention which comprises, as the outer 'or base layer thereof, liquid-containing means 60, a photosensitive layer 10 being supported by membrane 68 of said liquid-containing means. Separated from layer 78, by a permeable antiha'latiou'coating 12, is a, layer 14 of gelatin, polyvinyl alcohol, regenerated cellulose, hydroxyethyl cellulose, or other transparent, Water-permeable material wherein the positive image is adapted to be formed. Coating T2 is desirable but not essential, and layer 74 may adjoin layer 70 to ive satisfactory results. A backing or base 76, preferably of an opaque material such as paper, supports layer I4 and iorms'therewith the positive print material. The latter is secured to coating T2 so that it can be readily stripped therefrom when desired. To prevent gradual loss of developer by evaporation, the walls or cells 62 may be coated with water vapor-impervious material such as polyethylene or p'arafiin, or the film may be encased in a coating of said material. It is to be understood that layer 14 need not be transparent but may be formed of a relatively opaque material such as paper, in which event backing 16 may be dispensed with. It is also possible to form backing layer l6 c1 opal cellulose acetate and to provide layer 74 by regenerating the surface of the acetate sheet to cellulose.

It will now be apparent that any of the abovedescribed methods of forming a positive image by causing an image-forming component to be sensitive layer, in accordance with the development of the latter, and specifically the methods described in connection with the film of Fig. 1, may also be employed with the film structure of Fig. 3. Layer 10 is exposed through liquid-retaining means 50, which .is sufficiently homogeneous optically to be transparent, and after exposure the developing solution in cells 62 is released to saturate. said layer by :fracturing membrane 6 8. The development of layer It provides, in accordance with any of the hereinabove described methods, :a positive image in'layer 14. Thereaitenlay-ers M and 1.6 are stripped as a unit from the remainder of the. film. 'iThe positive 5 image which is thus formed in positive print material 14, I6 is not corrected for geometric reversal. However, the camera wherein the film is exposed may be provided with asuitable optical system for effecting optically the correction for reversal.

A modified form of liquid-containing means 60 is shown in Fig. 4 and comprises a sheet 92, for example, of film base provided with a plurality of chambers or cells 94, each of which'is connected by a self-sealing slot 96 to the bottom wall of :said base. Slots 96 'form temporary seals for said cells and a more permanent seal is provided by a frangible membrane 98 formed of a relatively brittle material and adapted to function in the same manner as membranes 42 and 68 of film-retaining means 38 and 60, respectively. When the side of film 92 containing slots 96 is subjected to sufficient tension to fracture sheet 98, slots 96 are also opened and the liquid contained in cells 94 is released.

The cells 94 of the retaining means of Fig. 4 may be filled with the liquid in any of several ways and one novel method comprises causing film 92 to travel over a roll lilll (Fig. 5) with the side thereof containing slots 96 on the outside, the tension on said film being insufficient to cause -slots 96 to open in the straight portions 92a thereof. Throughout the length of the curved portion 92b of said film, the outside surfaces are stretched a substantial amount so as to fully separate the walls of slots 96 and cells 94 remain open during the travel of the base around the roll until said base is again traveling in a straight line. Roll 100 is immersed in a bath I02 of the liquid so that all of curved portion 92b of base 92 is immersed in said liquid as well as short length of straight portions 92a of said film adjoining both ends of the curved portion. Cells 94 are thus filled during the curved travel of film 92, and because the straight travel of the film. is resumed beforethe latter emerges from bath I02, said cells are sealed prior to their emergence from the said bath and trap the liquid therein. The cells are thereafter permanently sealed by applying membrane 98 to film base 92. Various other methods may, of course, be used for filling the cells wi th the liquid.

i It will be noted that in each of the film structures described in Figs. 1 and 3, as well as in the modified liquid-containing means of Fig. 4, the liquid is released for saturating the photosensitive layer by fracturing a frangible liquid-retaining membrane. This may be accomplished by forming the membrane of a relatively more brittle material than the other layers of the film so that the fracturing of said -membrane can be achieved by subjecting the film to a tension which is beyond the yield point of said membrane and below the yield point of any of the other layers of. the film.

It will be apparent that the sheetlike liquidcontaining product of the present invention may be used to process otherphotosensitive layers Imerely'by substituting, in lieu of the silver halide developing agents contained therein, other known photographic developing agents capable of developing other photosensitive materials.

Since certain changes may be made in the above product without departing from the scope of the invention herein involved, it is intended that all matter contained in the above description or shown in the accompanying drawings shall be interpreted as illustrative and not in a limiting sense.

What'is claimed is:

1. A-composite photographic product containing at least one photographic chemical reagent and all of the liquid for rendering'said reagent effective to process an image in'a photoexposed, photographic, photosensitive element, said product being very thin in relation to'its length and breadth and comprising a pair of layers impervious to said liquid and superposed with respect to one another, all of said liquid being held-in said product between the outer surface portions of said layers and being confined within said product by said layers, one of said layers being substantially more frangible than the other so that the application of a given stress to both layers'of said product causes the rupture of said more frangible layer without rupturing the other layer, the liquid being releasable from said product depth wise through the fractures formed in said more frangible layer, said photographic chemical reagent being from the class consisting of the silver halide developers and the silver halide solvents.

2. A composite photographic'product containing at least a photographic Idevelopi'ng reagent and all of the liquid for rendering said reagent effective to develop an image in a photoexposed, developable, photographic, photosensitive element, said product being very thin in relation to its length and breadth and comprising a pair of layers impervious to said liquid and superposed with respect to one another, all of said liquid being held in said product between the outer surface portions of said layers and being confined within said product by saidlayers, one of said layers being substantially more frangible than the other so that the application of a given stress to both layers of said product causes the rupture of said more frangible layer without rupturing the other layer, the liquid being releasable from said product depthwise through the fractures formed in said more frangible, layer, said photographic developing reagent being a reducing agent for developing the exposed portion of a photographic element having as its photosensitive material a heavy metal salt capable of forming a latent image upon photoexposure and capable of being developed by said reducing agent to produce a visible image comprising the metal of said salt.

3. The product of claim 2 wherein the reagent is a developer for a silver halide emulsion.

4. The product of claim 2 wherein the reagent is a developer for a silver halide emulsion and the product also contains such other reagents as are required to so process a silver halide emul sion as to produce a transfer print of a latent image in said emulsion.

5. A compositephotographic product containing at least one photographicchemical reagent the liquid for rendering said reagent and all of I effective to process. an image in a photoexposed,

photographic, photosensitive element, said prodnot being very thin in relation to its length and breadth and comprising a pair of layers impervious to said liquid, and a third layer permeable to said liquid, said'layer's being superposed with respect to, one another, .all of said liquid being held in said product between'the'outer surface portions of said two impervious layers and being confined within said product by said impervious layers, one of said impervious layers being substantially more brittle than the other impervious layer so that the application of a given stress to both impervious layers of said product causes the rupture of said more brittle layer without rupturing the other impervious layer, the liquid being 7 releasable from said product 1111 .a depthwise dii-eetion through the rfraetures formed said more brittle layer, said permeable layer being lerated :on. the 53112 mi :said more brittle layer remote tron! the 'liouid :for the purpose of effecting a m uniform uist bution o said l u d upon .release the eo hrou h sai mo e br ttle layer,

a d rho oeranhie ohem a reagent e n a l one sub ance train he ci ss nsisting o the silver halide developers and the silver halide sol,- vents,

p od t i oleim r in h eage is eon ained in ol d term i said p m l aver and :is dissolved by said liquid as the latter p rmea s thr u h s d remeab e ayer- FL Th tro -riot o lenn fi b i the reagent is a developer for a silver halide emulsion.

18. A oomposite photographic produot contain? ne a lea ne photo aphic chem a e g and all. of the liouid for rendering said reagent 'ofizeetive to process an i-mage in a photoexpo'sed, photo raphic, photose sitive m sa d r d.- ue bein very t in ntenti o t gth a br adth and someth a hair o l yers im one o a d, ieud an u er osed w th pe o one no her, a o said i u d, be h d in sai modest etwe he o te u ace p rtions o said layers and b ng c nfin d with s id W d -le y sa d lev rs, o e oi sa d layers b in substantially more brittle than the other so that application of a given stress to both layers of said product causes the rupture .of said more brittle layer without rupturing the other layer, aid t r aye ha ing a p a ity f el ter (therein whidh hold the liquid, each cell having an outlet adjacent tosaid more brittle layer, the la ter s r ing a a s ew-re tor sealing h liquid :saidoells whereby the liquid is releasable from said produot depthwise upon the fracture of said itt e ever. s i Ph ograph c h mi al eag ein a le s ne ubsta ce rom e l s c nsisting lot the silver halide developers and the hal de so ent The product o oleim 8 he n t e s ls are arranged n row th re e ng a plu a ity o cel s in each row and the -ce 11 s of successive rows being staggered with respect to one another.

10. he roduct of claim 8 wherein each cell has a sols-sealing closure termed in the less britt e qu-i oo ta n iislave an s d more rit le lio'uidsretaining layer eonstitutes a further seal for said cells.

1.1, The product of claim 8 wherein a layer of materiai. pe m abl o s l u d, s su po e on the side o ai mor br lay r remote from the liquid for the purpose of elfeoting a more uniform distribution of said liquidupon release o said u i th ough s id m e r t e ayer.

1.2,. The product of claim 11 wherein the chemal agent s on aine sol d orm i h perm ab e a e and, the liq pa M1 sol n t Sam as it er at h o sai pe mea le la e r lease 3 moduet o c a m 12 h r i e hem.- i a ea ent is a si ve h lide d lo er a d the liqu d is wa er-- 1+1. The produc of laim 13 herein e iq on ains he ilv r hali de elo r in s u ion nd also contains a silver h de s l 15 A. composi e o raphi pr d c i n a as one ho g a ic he ica ea n and all of the liquid for rendering said reagent effective to process an image in a photoexposed, photographic, nhotosensi-tive element, said product being very thin in relation to its length and breadth and comprising at least three layers superposed with respect to one another, two of a d. levers be n im r ious to s id liqu d and nfinin said liqui ith aid p u a d h third f sa d layers e ng p r us nd o a in the liquid the pores thereof, said third layer being located betweensaid two impervious layers, one of said impervious layers being substantially more brittle than the other impervious layer so that the application .of a given stress to both impervious layers of said product causes the rope ture ofsaid more brittle impervious layer without rupturing the other impervious layer, the liquid being releasable ina depthwisedirection through the fractures formed in said more brittle i111; p r-vi e ever sa d phot a h c e ical reagent being at least one substance from the elass consisting of the Silver halide developers and the silver halide solvents.

16. The product of claim 15 wherein the re-.- agent .is a developing agent.

17. The product of claim 15 wherein the reagent is a developer for-a silver halide emulsion.

1B. The product of claim .15 wherein a fourth layer of material permeable to the liquid is supereoosed on the side of and adjacent said more brittle layer remote from the 'liquid-eontaining layer for the purpose of efieoting a more uniform distribution of said liquid upon release of said liquid through said more brittle layer.

19. The product of olaim 18 wherein the reagent is contained in solid form in said fourth layer for dissolution by said liquid as it travels therethrough.

References Cited in the file of this patent UN ED STATE P E Number Name Date Re. 20,843 Adler Sept. 6, 1938 1,075,210 Hey-l et a1 Oct. 7, 1913 1,592,379 Merle July 13, 1926 2,154,521 Max-n 1d Apr. 1 1939 0 3? v Ger r e u 4 2,299,694 Green ,T Oct. 20, 1942 2,304,939 Mfln es Dec. 15, 1942 2,315,966 Kn tt Apr. '6, 1943 2,322,005 Fierke June 15, 1913 2,322,005 Fierke l June 15, 1943 2,322,027 Jelley June 15, 1943 2,340,142 Banner Jan. 25, 194 1 2 4 ,64 t rs ay 19 2491 D oi o -'1 19 REIGN PATEN Number Country Date 567 011 G mmny 1 1 2, 1981 

1. A COMPOSITE PHOTOGRAPHIC PRODUCT CONTAINING AT LEAST ONE PHOTOGRAPHIC CHEMICAL REAGENT AND ALL OF THE LIQUID FOR RENDERING SAID REAGENT EFFECTIVE TO PROCESS AN IMAGE IN A PHOTOEXPOSED, PHOTOGRAPHIC, PHOTOSENSITIVE ELEMENT, SAID PRODUCT BEING VERY THIN IN RELATION TO ITS LENGTH AND BREADTH AND COMPRISING A PAIR OF LAYERS IMPERVIOUS TO SAID LIQUID AND SUPERPOSED WITH RESPECT TO ONE ANOTHER, ALL OF SAID LIQUID BEING HELD IN SAID PRODUCT BETWEEN THE OUTER SURFACE PORTIONS OF SAID LAYERS AND BEING CONFINED WITHIN SAID PRODUCT BY SAID LAYERS, ONE OF SAID LAYERS BEING SUBSTANTIALLY MORE FRANGIBLE THAN THE OTHER SO THAT THE APPLICATION OF A GIVEN STRESS TO BOTH LAYERS OF SAID PRODUCT CAUSES THE RUPTURE OF SAID MORE, FRANGIBLE LAYER WITHOUT RUPTURING THE OTHER LAYER, THE LIQUID BEING RELEASABLE FROM SAID PRODUCT DEPTHWISE THROUGH THE FRACTURES FORMED IN SAID MORE FRANGIBLE LAYER, SAID PHOTOGRAPHIC CHEMICAL REAGENT BEING FROM THE CLASS CONSISTING OF THE SILVER HALIDE DEVELOPERS AND THE SILVER HALIDE SOLVENTS. 